Production of anilin black upon vegetable textile fibers



- compounds, provided always UNITED STATES PATENT OFFICE.

EMILE AUGUSTE FOURNEAUX, OF MANCHESTER,

ENGLAND.

No Drawing. Application filed April 18,

To all whom it may concern 7 Be it known that I, EMILE AUGUs'rn FOURNEAUX, a subject of the King of Great Britain, residing at St. Jamess- Buildings, Oxford street, hTanchester, in the county of Lancaster, England, have invented new and useful Improvements in the Production of Anilin Black Upon Vegetable Textile Fibers, of which the following is a specification.

My invention relates to improvements in the. production of anilin black upon vegetable textile fibers.

My improved process consists in printing, padding or otherwise impregnating the fiber or fabric with anilin black mixtures of the composition specified below, developing the black by drying with hot air and completing the development and oxidation by subsequent treatment with a chromate. The analin black mixtures which I employ for the purpose consist of (a) Anilin alone or in admixture with ot er primary amins of the benzol series, comprising the homologues of anilin, the substitution products of anilin and their homologues, benzidin, its homologues and substitution products, but not diphenylamin that the proportion of such amins does not exceed three molecular proportions out of a total of eleven molecular proportions of amine;

(Z2) A strong mineral acid; the acids best suited for our purposes are hydrochloric acid or nitric acid or a mixture of both acids;

(0) F ormic acid in such proportion as may be required jointly with the strong mineral acid to prevent the formation of any material amount of undesirable brown by-products (03) A suitable thickening;

(c) Boracic acid for the purpose of preventing any undue loss of anilin during the drying operation. The boracic acid may be partly substituted by the phosphoric acids, preferably metaphosphoric acid;

(f) Chlorates of the alkali metals as oxidizing agents;

(g) An organic catalytic agent; paraphenylenediamin or its homologues, or paraaminophenol or its homologues;

(h) A mineral catalytic agent. For padding purposes preferably a soluble copper salt; for printing purposes a vanadium salt.

These anilin black mixtures are similar Specification of Letters Patent.

Patented Aug. 2-1, 1920. 1918. Serial No. 229,367.

in composition to themixtures employed in my previous U. S. Patent No. 1277056, August 27, 1918, but the two processes differ essentially in the following particulars,-

In the previous process the only oxidizing agents used are metallic chlorates. The oxidation of the bases to intermediary products of the nigranilin series and the condensation of these intermediary products with the bases to phenylazonium con'ipoiiinds take place partly during the drying process, but mainly during the subsequent steaming process, and they are allowed to proceed until virtually the whole of the compounds,

of the nigranilin series are transformed into triphenylazonium compounds, the true ungreenable anilin blacks.

In my present process the oxidizing action of the chlorates is intended to take place mainly or entirely during the drying process.

In carrying out this intention I have found it advantageous to allow the chlorate oxidation to stop somewhat short of the virtually complete condensation of the intermediary compounds of the nigranilin series with the bases to triphenylazonium compounds, and to complete the development and oxidation by treating the textile material subsequently with a solution'of a chromate.

It should be understood however that the chlorate oxidation must in any case be carried well beyond the nigranilin stage and it may be carried almost as far as in the previous process. In other words the composition of the black mixture should be such that the mixture of oxidation products formed in the course of the aging process consists largely of mono-, di-, and tri phenylazonium anilin blacks, though intermediary products of the may still be present. The composition of suitable mixtures is indicated in the examples given hereinafter.

As compared with the mixtures employed in my previous process the mixtures I now employ require a relatively higher proportion of the catalysts and of the strong mineral acid, but the proportion of the latter must not in any case exceed one-half of the amount required to neutralize completely the bases used. The proportion of chlorates now required is relatively less and may vary between six-twentieths and nine-twentieths molecular proportion for one molecular pronigranilin series portion of anilin or the corresponding proportion of mixtures of anilin with the other bases, as illustrated by the examples. The concentration of the chromate liquors re quired to complete the oxidation is determined by the composition of the black mixtures and may therefore be'regulated at will and according to requirements. Within these limits the most advantageous proportions of the several ingredients vary accord ing to the nature of the constituents and to other circumstances and for this reason I propose to give six typical mixtures under Examples 1 to 6, and I wish it to be understood that these mixturesmay be modified without materially affecting the results obtained on the lines indicated inthe previous British Specification No. 116562, corresponding to U. S. Patent No. 1277056.

My present process provides a useful alternative tothe process described in my previous U. S. Patent No. 1277056, August 27,

. 1918; as compared with other known processes depending on development by aging as contrasted with development by steaming my new process is both more expeditious and safer.

' I am aware of the previous use of boracic acid and of orthophosphoric acid in anilin mixtures not only as described in my previous U. SfPatent No. 1277056, August 27, 1918,'but also by Beltzer (Aniline Black and its Applications in Dyeing and Printing ,1 Noelting & Lehne, page 17 4:, published by Heywood & Company Limited of 150 Holborn, London in 1909).

My present process differs essentially from Beltzers' in thev composition of, the black mixtures and. in the subsequent treatmentof the fabric. 7

According to the above quotation the fabric impregnated withBeltzers black mixtures requires to be dried in a moist atniospherc at 70- degrees C. for about six hours, while a higher temperature endangers the fiber, whereas the fabric impregnated with our black mixtures may be safely dried at temperatures materially in excess of 70 degrees C. and the drymg may be completed wlthin a few minutes. This result could hardly have been anticipated a priori, and

marks a very substantial and important improvement;

From the foregoing it will be clearly understood that the use of boracic acid is only claimed in connection with anilin black mixtures of the composition and for the pur- 7 poses herein described.

I am aware of the fact that anilin black compounds such as I produce on the fiber by direct joint'oxidation of anilin and another primary aromatic amin havebeenproduced by the action of such amins on nigranilin, and I lay no claim to the latter process.

7 Examples.

W Example No. 1: Parts'by weight. Starch forty-five, gum dragon mucilage one hundred and eighty, anilin fifty-five and three quarters, hydrochloric acid (thirty-two de: grees Twaddell) twenty-one, paraphenylenediamindihydrochlorid five, formic acid (ninetyper cent.) seventy-five, boracic acid thirty, sodium chlorate twenty-seven and one-half, copper chlorid twelve and onequarter, water to bulk to one thousand, parts.

Example N0. 2: Parts by weight. Starch forty, gum dragon mucilage one hundred and sixty, anilin fiftysix and one eighth, hych'ochloric acid (thirty-two degrees T waddell) twenty-four and three-fifths, para phenylenediamindihydrochlorid five, formic acid (ninety per cent.) seventy, boracic acid thirty, sodium chlorate twentyefive and one half, copper chlorid twelve and'one quarter, water to bulk to one thousand parts.

Example No. 3 Parts by weight. Starch forty, gum dragon mucilage one hundred and sixty, anilin fifty-six, hydrochloric acid (thirty-two degrees 'lwaddell) twenty-seven and one half, paraphenylenediamindihydrochlorid four and one half, formic acid (ninety per cent.) seventy, boracic acid twenty-two and one-half, sodium chlorate twenty-one and one-half, copper chlorid twelve and one-quarter, Waterto bulk to one thousand parts;

Example No. 4: Parts by weight. Starch forty, gum dragon mucilage one hundred and sixty, anilin fifty-five and four-fifths, hydrochloric acid (thirty-two degrees Twaddell) thirty and three tenths, paraphenylenediamindihydrochlorid three and one-half, formic acid (ninety per cent.) thirty, b0- racic acid eighteen and three quarters, sodium chlorate nineteen and one-half, copper chlorid eleven and one-quarter, water 'to bulk to one thousand parts. 7

Example No. 5 Parts by weight. Starch thirty-six, gum dragon mucilage one hundred and fifty, anilin forty-one and twofifths, hydrochloric acid (thirty-two degrees Twaddell) nine, dianisidindihydrochloi'id sixteen,paraphenylenediamindihydrochlorid four, formic acid (ninety per cent.) sixtyfour, boracic acid twenty-five, sodium chlorate twenty-one and one-quarter, copper chlorid ten, water to. bulk to one thousand parts.

Example No. 6: Parts by weight. Starch sixty, gum dragon mucilage two hundred, anilin sixty-two, hydrochloric acid (thirtytwo degrees Twacldell) twenty-nine and onehalf, paraphenylenediamindihydrochlorid five and one-half, formic acid (ninety per cent.) fifty-one, boracic acid thirty-three, sodium chlorateth rty and one-half, vanadium chlorid seventeen of a solution of such concentration as to correspond to one part by weight of commercial ammonium vanadate in two hundred parts solution, water to bulk to one thousand parts.

In preparing the above mixtures the thickening agents should be made into a paste with part of the water and a little formic acid and boiled in the usual manner to form a thickening. The anilin, the acids and the salts of the bases may then be added to the warm thicknening and dissolved, then cool and add the sodium chlorate in solution.

The copper or vanadium salt should only be added immediately before use.

The mixture described in Example No. 6 is intended for printing, the others for impregnating the fiber or fabric by means other than printing. The fiber or fabric impregnated with the anilin black mixture is dried by means of hot air in any of the well-known drying and oxidizing chambers commonly used for the purpose, the process being conducted in the ordinary manner, but the tem perature of the drying chamber may safely exceed 70 degrees Centigrade. By providing sufficient drying capacity the drying and aging operations may be completed within approximately ten minutes. The vegetable fiber or fabric is finally treated with a solution of a chromate in the usual manner. Calculated as sodium bichromate the quantity of chromate (in parts by weight) required for the treatment of a quantity of fiber or fabric which has retained one thousand parts by weight of any of the several mixtures described in the above examples is approximately as follows :five for No. 1, nine for No. 2, fifteen for No. 3, eighteen for No. 4:, ten for No. 5, six for No. 6.

Having now particularly described and ascertained the nature of my said invention and in what manner the same 'is to be performed, I declare that what I claim is 1. A process of producing black upon vegetable textile fibers which consists in impregnating the fiber with a solution comprising anilin, a strong mineral acid, formic acid, a thickener, boracic acid, chlorates of the alkali metals, an organic catalytic agent, an inorganic catalyst, then developing by drying with hot air and finally by chroming.

2. A process of producing black upon vegetable textile fibers which consists in impregnating the fiber with a solution comprising anilin, a strong mineral acid, formic acid, a thickener, boracic acid, chlorates of the alkali metals, an organic catalytic agent, an inorganic catalyst, all in the proportions specified, then developing by drying with hot air, and finally by chroming.

3. A dyeing solution, comprising anilin and an admixture of other primary amins of the benzol series the proportion of such amins not exceeding three molecular proportions out of a total of eleven molecular proportions, a mineral acid, formic acid, a thickener, boracic acid, chlorates of the alkali metals, paraphenylenediamin, and a soluble copper salt.

4. A dyeing and printing mixture, comprising starch, gum dragon mucilage, anilin, hydrochloric acid, paraphenylenediamindihydrochlorid, formic acid, boracic acid, so dium chlorate, a mineral catalytic agent, and water, all in the proportions specified.

5. i dyeing solution comprising the fol lowing components in the proportions by weight as stated, starch forty-five, gum dragon mucilage one hundred and eighty, anilin fifty-five and three quarters, hydrochloric acid (thirty-two degrees Twaddell) twenty-one, paraphcnylenediamindihydrochlorid five, formic acid (ninety per cent.) seventy-five, boracic acid thirty, sodium chlorate tventy-seven and one-half, copper chlorid twelve and one-quarter, water to bulk to one thousand parts.

6. A dyeing solution comprising anilin, a strong mineral acid, formic acid, thickening, boracic acid, metaphosphoric acid, chloratcs of the alkali metals, an organic catalytic-agent, an inorganic catalyst, all in the proportions specified.

In testimony whereof I have signed my name to this specification.

EMILE AUGUSTE FOURNEAUX. 

